High efficiency quantum well waveguide solar cells and methods for constructing the same

ABSTRACT

Photon absorption, and thus current generation, is hindered in conventional thin-film solar cell designs, including quantum well structures, by the limited path length of incident light passing vertically through the device. Optical scattering into lateral waveguide structures provides a physical mechanism to increase photocurrent generation through in-plane light trapping. However, the insertion of wells of high refractive index material with lower energy gap into the device structure often results in lower voltage operation, and hence lower photovoltaic power conversion efficiency. The voltage output of an InGaAs quantum well waveguide photovoltaic device can be increased by employing a III-V material structure with an extended wide band gap emitter heterojunction. Analysis of the light IV characteristics reveals that non-radiative recombination components of the underlying dark diode current have been reduced, exposing the limiting radiative recombination component and providing a pathway for realizing solar-electric conversion efficiency of 30% or more in single junction cells.

RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent applicationSer. No. 13/587,530, filed Aug. 16, 2012, entitled HIGH EFFICIENCYQUANTUM WELL WAVEGUIDE SOLAR CELLS AND METHODS FOR CONSTRUCTING THESAME, which claims the benefit of U.S. Provisional Application Ser. No.61/525,707, filed Aug. 19, 2011, entitled HIGH EFFICIENCY QUANTUM WELLWAVEGUIDE SOLAR CELLS AND METHODS FOR CONSTRUCTING THE SAME, the entiredisclosure of each of which applications is herein incorporated byreference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with U.S. government support under Grant NumberNNX110E59P, awarded by the National Aeronautics and Space Administration(NASA) and Grant Number ERDA1-0000021389 awarded by the New York StateEnergy Research and Development Authority (NYSERDA). The government mayhave certain rights in this invention.

FIELD OF THE INVENTION

This invention relates to semiconductor-based photovoltaic energyconverters, also known as “solar cells,” and to the design andfabrication of the same.

BACKGROUND OF THE INVENTION

With appropriate electrical loading, photovoltaic solid statesemiconductor devices, commonly known as solar cells, convert sunlightinto electrical power by generating both a current and a voltage uponillumination. The current source in a solar cell is the charge carriersthat are created by the absorption of photons. These photogeneratedcarriers are typically separated and collected by the use of PN or PINjunctions in semiconductor materials. The operational voltage of thedevice is limited by the dark current characteristics of the underlyingPN or PIN junction, among other limiting characteristics. Thus improvingthe power output performance of any solid state solar cell generallyentails simultaneously maximizing absorption and carrier collectionwhile minimizing dark diode current.

Quantum well solar cells seek to harness a wide spectrum of photons athigh voltages in a single junction device by embedding narrow energy-gapwells within a wide energy-gap matrix. By avoiding the limitations ofcurrent matching inherent in multi junction devices, quantum wellwaveguide solar cells have the potential to deliver ultra-highefficiency over a wide range of operating conditions. Quantum well solarcells have been demonstrated in a variety of different material systems,and the basic concept has been extended to include quantum dots. Clearimprovements in lower energy spectral response have been experimentallyconfirmed in both quantum well and quantum dot solar cells. However,photon absorption, and thus current generation, is hindered inconventional quantum structured solar cells by the limited path lengthof incident light passing vertically through the device. Moreover, theinsertion of narrow energy-gap material into the device structure oftenresults in lower voltage operation, and hence lower photovoltaic powerconversion efficiency.

Optical scattering into laterally propagating waveguide modes provides aphysical mechanism to dramatically increase photocurrent generation inquantum well solar cells via in-plane light trapping. The refractiveindex contrast in a typical quantum well solar cell provides lateraloptical confinement and naturally forms a slab waveguide structure.Coupling of normally incident light into lateral optical propagationpaths has been reported to lead to increases in the short circuitcurrent of InP/InGaAs quantum well waveguide solar cells coated withnanoparticles. However, maintaining high open circuit voltage remains auniversal challenge for all quantum well and quantum dot solar celldevices. It is therefore desirable to provide a device with a novelmaterial structure to achieve high open circuit voltages.

SUMMARY OF THE INVENTION

This invention overcomes the disadvantages of the prior art by providinga solar cell design and process for constructing a solar cell thatemploys an extended region of wide energy gap material within thedepletion region adjacent to the emitter and incorporating step-gradedquantum wells. This structure enhances the open circuit voltage ofquantum well waveguide solar cell structures. Advanced quantum wellsolar cell structures both minimize the underlying diode dark currentsand increase the optical path length to deliver solar electricconversion efficiencies exceeding 30% over a wide range of spectralconditions.

In an illustrative embodiment, a conventional homojunction structureincorporates an InGaAs well embedded within a GaAs matrix. To reduce thediode dark current, wider energy-gap InGaP and AlGaAs material isemployed in the emitter and inserted into the depletion region adjacentto the emitter, forming an extended wide band gap emitter heterojunctionstructure. Illustratively, the refractive index contrast is furtherenhanced by employing an AlGaAs base layer.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention description below refers to the accompanying drawings, ofwhich:

FIG. 1 is a schematic cross-sectional side view of a thin film solarcell device according to an illustrative embodiment incorporating alower band gap, waveguiding absorption layer and optical coatings toincrease the optical path length of incident light through the activeregion of the device;

FIG. 2 is a graphical diagram of the approximate refractive index as afunction of position profile for three different InGaAs quantum wellwaveguide solar cell structures, in accordance with the illustrativeembodiment;

FIG. 3A is a graphical diagram of the photoluminescence spectra from anInGaAs quantum well solar cell structure having GaAs as a basestructure, according to the illustrative embodiment;

FIG. 3B is a graphical diagram of the photoluminescence spectra from anInGaAs quantum well solar cell structure having AlGaAs as a basestructure, according to the illustrative embodiment;

FIG. 3C is a graphical diagram of the light voltage and current (“IV”)characteristics from an InGaAs quantum well solar cell structure havingGaAs as a base structure, according to the illustrative embodiment;

FIG. 3D is a graphical diagram of the light IV characteristics from anInGaAs quantum well solar cell structure having GaAs as a basestructure, according to the illustrative embodiment;

FIG. 4 is a graphical diagram of the short circuit current density as afunction of open circuit voltage derived from illuminated IVmeasurements on two different quantum well structures, according to theillustrative embodiment;

FIG. 5 is a graphical diagram of the saturation current density as afunction of quantum well energy for an InGaAs quantum well solar cellwith an extended heterojunction, according to the illustrativeembodiment;

FIG. 6 is a graphical diagram of the short circuit current as a functionof base layer energy gap for both coated and uncoated devices, accordingto the illustrative embodiment; and

FIG. 7 is a graphical diagram of IV curves comparing conventional GaAssolar cell performance to an InGaAs quantum well structure, according tothe illustrative embodiment.

DETAILED DESCRIPTION

A typical thin film solar cell structure contains a limited volume oflow band gap material, and thus requires advanced light trappingstructures to reach its potential performance levels. Light managementis achieved by assuring that incident photons are not lost due toreflections but are instead directed into the semiconductor absorbinglayers. The scattering of incident light to ensure each photon has anon-normal trajectory is a strategy for increasing the optical pathlength of photons within the absorption layer. In addition, theapplication of a back reflector to bounce any unabsorbed photons back upinto the active layers of the device is a beneficial aspect of anyeffective photovoltaic light trapping scheme. However, the mosteffective light trapping schemes will also direct light horizontallyinto the plane of the absorbing layer. Waveguide structures in whichthin layers of high refractive index material are surrounded by lowrefractive index material provide a physical mechanism by which toachieve this type of in-plane light trapping.

A schematic diagram of an exemplary waveguide solar cell structure isdepicted in FIG. 1. This thin film waveguide solar cell incorporateslower band gap, higher index of refraction materials in the activeregion of the device, along with tailored, nanostructured opticalcoatings. The optical path length of light incident upon this noveldevice is dramatically enhanced via coupling into laterally propagatingwaveguide modes. This combination of active device structure and passivecoatings redirects normally incident light into laterally propagatingwaveguides modes, and represents a dramatic change in thin film solarcell design.

With reference to FIG. 1, a thin film waveguide photovoltaic device 100is depicted according to an illustrative embodiment. In operation,incident light 101 first encounters a top covering surface 110, whichcan be a top cover glass, transparent epoxy or other light transmittingcovering surface. A front anti-reflective coating 105 is applied to thetop covering surface according to an illustrative embodiment. The topcovering surface 110 is located above a PIN diode semiconductor materialdevice structure 130. The PIN diode structure is coated with atransparent optical coating 120 that minimizes reflection losses andscattering incident light into the underlying PIN diode 130. For a moredetailed description of methods for the construction of the topantireflective coating 120, refer to commonly assigned provisionalpatent application Ser. No. 13/528,792, filed Jun. 20, 2012, entitledLATERALLY SCATTERING ANTIREFLECTIVE COATINGS AND METHODS OFMANUFACTURING THE SAME, by Welser, et al., the teachings of which areincorporated by reference as useful background information.

The refractive index of the top optical coating 120 is illustrativelyadapted to generate a graded index of refraction antireflection coating,consisting of one or more layers with refractive index intermediatebetween the covering surface material 110 and the PIN diodesemiconductor material 130. In an illustrative embodiment one or more ofthe layers in the top optical coating 120 also incorporate nanoparticlesor nanorods which differ in refractive index from that of theirsurrounding material. Nanostructured optical coatings 120 provide amechanism by which incident light can be scattered horizontally into theplane of the underlying PIN diode 130.

In the illustrative embodiment shown in FIG. 1, the PIN diode devicestructure consists of top window/contact layers 132, back surfacefield/contact layers 136, and incorporates lower energy gap material 134within the depletion region of the PIN diode structure 130. Lower energygap material also tends to have a higher index of refraction, therebyresulting in the formation of a waveguide structure. The PIN diodedevice structure can consist of any common semiconductor materials,including but not limited to group IV materials (Si, Ge, SiGe, SiC,etc.), group III-V materials (GaAs, AlGaAs, InGaP, InGaAs, InP, AlInAs,GaAsSb, InAsSb, AlAsSb, GaN, InGaN, AlGaN, etc.), group II-VI materials(CdS, CdTe, etc.), and group I-III-VI₂ materials (CIGS, etc.). Inanother illustrative embodiment, the PIN diode device structure 130comprises two or more PIN junctions. In yet another illustrativeembodiment, the refractive index and thickness of the semiconductormaterials used in the top window/contact layers 132 is tailored tofunction as part of a step graded refractive index antireflectionstructure. Electrical contact is made to the top window/contact layers132 via metal contacts 125.

In the illustrative embodiment shown in FIG. 1, the back of thesemiconductor PIN diode 130 is coated with a conductive, transparentoptical coating 140. In an illustrative embodiment, the refractive indexof the bottom optical coating 140 has a value of approximately 1.5 orlower, thereby creating an Omni-directional reflector when combined withthe underlying metallic layer 150. In another illustrative embodiment,the bottom optical coating 140 consists of multiple layers differing inrefractive index to form a distributed Bragg reflector. In yet anotherillustrative embodiment one or more of the layers in the bottom opticalcoating 140 also incorporate nanoparticles or nanorods. In yet anotherillustrative embodiment, the back-scattering structure, consisting ofthe back optical coating 140 and back metal contact 150, employplasmonic structures. Plasmonic structures closely coupled to absorbingsemiconductors can be used to increase the photocurrent in a variety ofthin film solar cells. In particular, the peak wavelength of the plasmonresonance is adjustable to match the absorption band of the nearbysemiconductor layers, particularly the lower band gap, higher indexmaterial 134. For a more detailed description of methods for theconstruction of the back reflector structure 140, 150, refer to commonlyassigned provisional patent application Ser. No. 13/528,581, filed Jun.20, 2012, entitled DIFFUSE OMNI-DIRECTIONAL BACK REFLECTORS AND METHODSOF MANUFACTURING THE SAME, by Welser, et al., the teachings of which areincorporated by reference as useful background information.

In the illustrative embodiment shown in FIG. 1, optical scattering bythe nanoparticles or nanorods above the semiconductor device structurecan lead to coupling of photons incident normal to the device surfaceinto lateral optical propagation paths, i.e., paths parallel to thedevice surface. These parallel optical modes 170 result from theintroduction of a lateral wave vector component into the forwardscattered wave 160, and can dramatically enhance the optical path lengthof photons through thin film solar cell device structures. Unabsorbed,lower energy photons that are not coupled into the waveguide modes 170pass through the PIN diode 130 device before striking a back scatteringoptical coating 140. Back-scattered light 180 is directed into theactive, absorbing layers of the device by the presence of theback-scattering structure, which consists of the back optical coating140 and back metal contact 150.

According to various embodiments, the front optical coating 120 isconfigured and arranged with transparent antireflection coatingstructures to reduce the reflection of incident photons at the materialinterface between the light transmitting covering surface 110 andsemiconductor device structure 130. The back optical coating 140 isconfigured and arranged to maximize the reflection of unabsorbed photonsback into the semiconductor device structure. In the variousembodiments, the front coating 120 and the back coating 140 areimplemented in accordance with industry standard processes and materialsknown to those skilled in the art. These materials include, but are notlimited to, titanium dioxide, silicon dioxide, indium tin oxide, zincoxide, and other transparent conductive oxides (TCOs). Theantireflection coating can be synthesized using a variety of techniques,including sputtering, evaporation, and oblique-angle deposition.Transparent antireflection coating structures can comprise a singlelayer or multiple layers of materials having an index of refractionintermediate between the semiconductor structure 140 and the media inwhich the incident photons are delivered, which by way of example isillustrated as a cover glass or encapsulant 110 in FIG. 1. Backreflector structures can comprise either a single metallic layer, or aplurality of layers consisting of a metallic layer in combination withone or more layers of transparent optical material having an index ofrefraction lower than the semiconductor material. In particular,Omni-directional reflectors (ODRs), which combine a metal layer with alow-refractive index layer, provide ultra-high reflectivity over a widerange of wavelengths and incident angles.

According to an illustrative embodiment, the refractive index of thevarious layers is as follows: the front antireflective coating 105 has arefractive index of n˜1 to 1.5, the cover glass or encapsulant 110 ofn˜1.5, the forward scattering antireflection coating 120 of n˜1.5 to 3,the top window contact layer 132 of n˜3, the PIN diode with lower bandgap, higher index material 134 of n˜3.8, the back surface field contactlayer 136 of n˜3, and the back scattering optical coating of n˜1.1. Therefractive index of the various layers is variable within ordinary skillto achieve the desired functionalities as described herein.

When light is incident upon a semiconductor device coated with acontinuous thin film material, the forward- and back-scattered light iswell known to depend upon the optical properties of the thin film andsurrounding environments which dictate the reflection, refraction, andabsorption characteristics of the light. Employing an array ofnanoparticles or nanorods can provide unique and desirable physicalphenomena, particularly when the particle size is very small compared tothe incident wavelength. In this case, the scattering and absorptioncharacteristics of the forward wave front depend upon the size, shape,density, and permittivity of the nanoparticles. See for example, by wayof useful background information, P. Matheu, S. H. Lim, D. Derkacs, C.McPheeters, and E. T. Yu, Metal and dielectric nanoparticle scatteringfor improved optical absorption in photovoltaic devices, Appl. Phys.Lett. 93, 113108-1-3 (2008). Nanoparticle coatings can provideadditional light-trapping benefits when the adjoining semiconductordevice structure contains distinct index of refraction steps. In thiscase, optical scattering by nanoparticles atop a semiconductor devicestructure can lead to coupling of photons incident normal to the devicesurface into lateral optical propagation paths, i.e., paths parallel tothe device surface. These parallel optical modes result from theintroduction of a lateral wave vector component into the scattered wave,and can dramatically enhance the optical path length of photons throughthin film solar cell device structures.

Oblique-angle deposition is a method of growing arrays of nanorods in awide variety of materials, enabled by surface diffusion andself-shadowing effects during the deposition process. Because theresulting thin films are porous, oblique-angle deposition is utilized asan effective technique for tailoring the refractive index of a varietyof thin film materials (see for example, by way of useful background,J.-Q. Xi, M. F. Schubert, J. K. Kim, E. F. Schubert, M. Chen, S.-Y. Lin,W. Liu, and J. A. Smart, Optical Thin-Film Materials with Low RefractiveIndex for Broad-Band Elimination of Fresnel Reflection, Nat. Photon.,vol. 1, pp. 176-179, 2007). In one illustrative embodiment, the bottomoptical coating 140 comprises of a layer nanostructured, porous indiumtin oxide layer with a refractive index of 1.5 or lower deposited byoblique angle deposition. In another illustrative embodiment, the topoptical coating 120 comprises multiple layers, with at least one layerof dense indium tin oxide and at least one layer of porous indium tinoxide or porous titanium dioxide deposited by oblique-angle deposition.

In another illustrative embodiment, the top optical coating 120 and thebottom optical coating 140 comprise dielectric and/or metallicnanoparticles embedded within a dense optical film material. Examplesinclude SiO₂ nanoparticles embedded within a dense layer of indium tinoxide, SiO₂ nanoparticles embedded within a dense layer of TiO₂, TiO₂nanoparticles embedded within a transparent encapsulant, TiO₂nanoparticles embedded within a dense layer of SiO₂, and metallicnanoparticles embedded within a dense layer of ITO. Note that depositionof the nanoparticles can occur according to conventional techniques inillustrative embodiments.

The operating voltage of a semiconductor PIN diode solar cell 130 isgenerally dictated by the underlying dark diode current of the device.The dark diode current of semiconductor devices is composed of severaldifferent components, all of which are dependent upon the energy gap ofthe material used in the active junction of the device. Typically, eachcell in a solar cell consists of one type of material, and the energygap of that material influences both the current and voltage output ofthe device. Lower energy gap material can enhance the current generatingcapability, but typically results in a lower operating voltage.Therefore, it is desirable to provide a device structure 130 that canharness the current generating capabilities of narrow energy gapmaterial while also maintaining a high operating voltage.

Reference is now made to FIG. 2, showing a graphical diagram 200 of theapproximate refractive index as a function of position profile for threedifferent InGaAs quantum well waveguide solar cell structures, accordingto the illustrative embodiment. An extended region of wide energy gapmaterial is employed within the depletion region adjacent to the emitterand incorporates step-graded quantum wells. For a detailed descriptionof structures of quantum wells, refer to commonly assigned U.S. patentapplication Ser. No. 12/985,748, filed Jan. 6, 2011, entitled QUANTUMWELL WAVEGUIDE SOLAR CELLS AND METHODS OF CONSTRUCTING THE SAME, byWelser et al., the teachings of which are incorporated by reference asuseful background information. In a conventional homojunction structure,an InGaAs well is embedded within a GaAs matrix, resulting in arefractive index profile such as that shown with the triangle-dashedline 210 in FIG. 2. To reduce the diode dark current below that obtainedin conventional structures, wider energy-gap InGaP and AlGaAs materialis employed in the emitter and inserted into the depletion regionadjacent to the emitter, forming an extended wide band gap emitterheterojunction structure. Other materials can be employed asconventionally available and employed by those having ordinary skill toachieve the desired functionalities. The circle-dashed line 220 in FIG.2 illustrates this second type of quantum well structure. To furtherenhance the refractive index contrast around the InGaAs well, a thirdstructure employs an AlGaAs base layer, as shown by the solid black line230 in FIG. 2.

The InGaAs quantum well solar cell structures described herein areillustratively synthesized via metal-organic chemical vapor deposition(MOCVD) by Kopin Corporation. Any appropriate chemical vapor depositiontechnique can be employed, as readily apparent to those having ordinaryskill. Single InGaAs quantum wells with a target thickness ofapproximately 33 nm are located within the built-in field of thejunction depletion region. A step-graded InGaAs compositional profile isemployed to form a series of smaller energy steps (˜35 meV) thatphotogenerated carriers can overcome to escape from the potential well.The effective energy gap of the InGaAs well is a function of both thewell compositional profile and thickness, and can be quantified byphotoluminescence (PL) emissions. The illustrative structures arecharacterized by PL measurements generated with excitation from both 532nm and 785 nm laser sources.

Small, simple mesa test devices are fabricated with standard wet etchchemistry and photolithography to define devices with junction area assmall as approximately 75 μm×75 μm. A variety of tests can be performedon these devices, including measuring dark current versus voltage,capacitance versus voltage, and illuminated current versus voltagemeasurements. For light I-V measurements, the photocurrent is generatedby illumination with an un-calibrated halogen lamp through a probestation microscope that can be varied in intensity. A test structureconsisting of a device with a junction area of approximately 200 μm×340μm and an open aperture of approximately 120 μm×260 μm is used tomeasure the illuminated current versus voltage characteristics of allthree structures. In addition, the extended heterojunction structurewith a GaAs base has been re-grown and fabricated into a larger, nearly500 μm×500 μm device. Specifically, the larger device has a junctionarea of approximately 0.2236 mm², and an aperture area that is nearly98.4% of the junction area. While the results obtained from the smallerdevices are consistent with the larger devices, the larger relativeaperture size of the 500 μm×500 μm device enables the illuminated I-Vperformance to be characterized at slightly higher current densities.

The photoluminescence spectra and light IV characteristics from the twoInGaAs quantum well solar cell structures employing an extended wideenergy-gap emitter are shown in FIGS. 3A-3D. More specifically, FIG. 3Ais a graphical diagram of the photoluminescence spectra from an InGaAsquantum well solar cell structure having GaAs as a base structure. FIG.3B is a graphical diagram of the photoluminescence spectra from anInGaAs quantum well solar cell structure having AlGaAs as a basestructure. FIG. 3C is a graphical diagram of the IV characteristics froman InGaAs quantum well solar cell structure having GaAs as a basestructure. FIG. 3D is a graphical diagram of the IV characteristics froman InGaAs quantum well solar cell structure having GaAs as a basestructure.

As shown in FIGS. 3A and 3B, in both structures, the PL emission fromthe step-graded InGaAs well peaks (316, 326) near 1.30 eV, while theextended AlGaAs emitter material luminescence peaks (317, 327) around1.72 eV. The base layer emissions differ, as expected, with a peak 318near 1.42 eV for the GaAs base structure line 315 and a peak 328 ofapproximately 1.52 eV for the AlGaAs base structure line 325.

Overall, the illuminated current-voltage characteristics 330, 340 shownin FIGS. 3C and 3D of the two emitter heterojunction structures arequite similar. Small area test devices on both structures exhibit fillfactors near 83%, short circuit current density (J_(sc)) on the order of25 mA/cm² at maximum halogen lamp intensity, and open circuit voltage(V_(oc)) approaching 1.05 V. These open circuit voltage values arehigher than the V_(oc)˜0.97 V obtained on the control structure withoutthe extended heterojunction, and comparable to the V_(oc) ofstate-of-the-art bulk GaAs single junction cells, despite the additionof a narrower energy gap InGaAs well.

To further quantify the voltage characteristics of the InGaAs quantumwell waveguide solar cells, the short circuit current at varying whitelight intensities have been analyzed as a function of open circuitvoltage. The J_(sc)-V_(oc) curve that results from characterizing andplotting the short circuit current as a function of open circuit voltageprovides an effective measurement of the underlying dark diode current,unencumbered by the effects of series resistance. FIG. 4 illustrates agraphical diagram 400 that compares the diode current 410 of aconventional structure to the diode current 420 of the InGaAs quantumwell structure with a GaAs base layer and an extended heterojunctionfabricated into a 0.2236 mm² device. A dramatic reduction in the n=2space charge recombination is observed (412), allowing the n=1saturation current density (J_(o1)) to be extracted from a two-diode fit(422) of the short circuit current versus open circuit voltage data. Thediode fit assumes the underlying dark current can be described as thesum of two diodes at room temperature (25° C.), one with an idealityfactor of one (n=1) as line 410 and the other with an ideality factor oftwo (n=2) as line 420. Diode fits indicate that the n=1 saturationcurrent density of the diode current can be reasonably fit asJ_(o1)=4.5×10⁻¹⁷ mA/cm² for both InGaAs quantum well solar cellsemploying an extended heterojunction.

While Shockley injection typically limits the n=1 component of bulkIII-V diodes, radiative recombination within the InGaAs quantum wellcould also play a role. Indeed, the observed lack of sensitivity of thevoltage characteristics to the addition of aluminum to the base layermay suggest that radiative limits have been reached at 1-sun bias levelsin quantum well solar cells employing an extended heterojunctionstructure. The concept of detailed balance is a well established meansof computing the expected radiative current that should limit theperformance of photonic devices. As noted by Henry (see, for example, C.H. Henry, “Limiting Efficiencies of Ideal Single and Multiple Energy-gapTerrestrial Solar Cells,” J. Appl. Phys., vol. 51, pp. 4494-4500, August1980), the n=1 saturation current density (J_(o1)) in the radiativelimit should equal the thermal radiation current (J_(th)), such that:

$\begin{matrix}{J_{th} = {( \frac{{q( {n_{cell}^{2} + 1} )}{kTE}_{g}^{2}}{4\;\pi^{2}\hslash^{3}c^{2}} ){\exp( {{- E_{g}}/{kT}} )}}} & (1)\end{matrix}$where E_(g) corresponds to the peak energy of the photons emitted attemperature T. An absorbing bottom substrate is assumed in Equation (1),with photons escaping via the top surface into a media with a refractiveindex (n_(top)) of one (e.g. air). Following the teachings of Henry, itis assumed in Equation (1) that the refractive index of the cell(n_(cell)) and the bottom substrate (n_(bottom)) are both equal to thatof GaAs (n_(GaAs) ˜3.5). Assuming an effective energy gap of 1.3 eV forthe InGaAs well, Equation (1) implies J_(o1)=1×10⁻¹⁵ mA/cm², which isnearly an order and a half higher in magnitude than the value inferredfrom measurements on InGaAs quantum wells with an extendedheterojunction structure. This indicates that the InGaAs quantum wellstructures are actually operating in a regime of suppressed radiativerecombination.

A number of different physical mechanisms can lead to a suppression inradiative current relative to that predicted by Equation (1), includingthe finite volume of the InGaAs well, photon recycling, andperturbations in the diode quasi-Fermi level. Photon recycling is anintriguing phenomenon that can be leveraged to further reduce the darkcurrent and hence increase the operation voltage of InGaAs quantum wellsolar cells operating in the radiative limit. Radiative emissions can besuppressed in structures which support the re-absorption of emittedphotons by reflecting emitted photons back into the absorber region ofthe device. In the devices described herein, such photon recycling isexpected to be negligible due to basic geometrical considerationsassociated with fabricating test structures with limited lateraldimensions on a relatively thick substrate (˜625 μm). However, photonrecycling effects can be greatly enhanced by removing the GaAs substrateand fabricating devices with a thin-film architecture. Back reflectionsand photon recycling are further enhanced by the use of anomni-directional back reflector incorporating a low index film betweenthe substrate and the back metal (such as coating 140 of FIG. 1). FIG. 5illustrates a graphical diagram 500 of the potential reduction in darkcurrent that is realized by fabricating InGaAs quantum well solar cellswith an extended heterojunction in a thin-film format which promotesefficient light trapping. The dashed line 510 represents the results ofa traditional detailed balance calculations (for example as articulatedby Henry hereinabove) assuming optically thick cells and an absorbingsubstrate. The solid lines 520, 530 and 540 represent a modified modelthat employs extended wide band gap emitters and projecting the impactof photon recycling.

Enhanced light trapping, in addition to providing an avenue to furthersuppress radiative recombination, is leveraged to dramatically increasethe short circuit current of thin film solar cells. Photon absorption,and thus current generation, is typically hindered in conventional thinfilm solar cell designs, including quantum well structures, by thelimited path length of incident light passing vertically through thedevice structure. FIG. 6 illustrates a graphical diagram 600 of theprojected short circuit current of InGaAs waveguide solar cellsemploying a single 33 nm well with an absorption edge at 950 nm (˜1.3eV) embedded within a 0.5 μm higher energy gap base layer. Thecalculations summarized in FIG. 6 employ realistic estimates of theabsorption coefficient and assume the solar spectrum can be approximatedby that of a 5800K blackbody. Under these conditions, the short circuitcurrent of uncoated cells typically decreases slightly with increasingbase layer energy gap, as shown by line 610. Applying a standardtwo-layer antireflection (AR) coating to the front surface and employinga simple reflector at the back surface to double the optical path lengthis shown at line 620 to nearly double the short circuit current. Shortcircuit currents approaching 40 mA/cm² are projected for devices with1.3 eV wells that employ more advanced light trapping structures toleverage the waveguide properties of the quantum well structure andfurther increase the optical path length. Even higher short circuitcurrents are shown as line 630 from light trapping structures employinglower energy gap wells. We note that AM0 (and AM1.5) efficiencies inexcess of 30% can be achieved in devices that can combine J_(o1) valueson the order of 1×10⁻¹⁸ mA/cm² with J_(sc) values above 40 mA/cm² (or 32mA/cm²).

Conventional state-of-the-art GaAs solar cells output nearly 34 mA/cm²of current at a V_(oc) just over 1.04 volts under AM0 illumination,yielding a solar-electric conversion efficiency approaching 22%.Increasing the efficiency to 30% in space environments requires noveldevice designs that can boost both the current and voltage output. TheInGaAs quantum well structures with an extended wide band gap emitterdescribed herein have the ability to increase both the operating voltageand current of GaAs-based solar cells. By suppressing both non-radiativeand radiative recombination, the underlying dark current is dramaticallyreduced and the operating voltage of the device is increased. Theaddition of lower energy gap InGaAs also raises the current generatingcapability of GaAs-based solar cells. However, to achieve enhancedcurrent output, advanced light trapping techniques are desirablyincorporated into the overall device design.

Photon absorption, and thus current generation, is hindered in quantumwell structures by the limited path length of incident light passingvertically through the device structure. Optical scattering into lateralwaveguide structures provides a physical mechanism to dramaticallyincrease photocurrent generation through in-plane light trapping.Moreover, lateral waveguide modes can be enhanced by the higherrefractive index of the InGaAs well.

The application of light trapping structures both above and below theactive region can increase the optical path length of lower energyphotons through the quantum wells. Light trapping can also reduceradiative recombination, and thus further increase the operating voltageof InGaAs quantum wells with extended wide band gap emitters, via thewell-established phenomena of photon recycling. Nanostructured opticalcoatings offer unique methods for engineering the optical properties ofthin film coatings.

Nanostructured indium tin oxide (ITO) with low refractive index (n) canbe employed in omni-directional reflector (ODR) structures consisting ofa low-n dielectric/metal film bilayer. ODRs combine theomni-directionality of metal films with the high peak reflectivity of adistributed Bragg reflector (DBR), and can function as ahigh-performance back reflector in an InGaAs quantum well waveguidesolar cell. Mie scattering from the nanostructured ITO layer can alsoenhance the coupling of long wavelength photons into the lateralwaveguide modes of the quantum well absorber layer.

FIG. 7 shows a graphical diagram 700 of the projected performance of a30% efficient device employing both an InGaAs quantum well/extended wideband gap emitter and advanced light trapping structures. Conventionalstate-of-the-art GaAs solar cells collect approximately 85% of thecurrent available in an AM0 space spectrum above approximately 1.42 eV,the band gap of the GaAs absorber layer. Significant increases in thecurrent output 710 of conventional designs are unlikely, as much of thecurrent loss is due to reflection and absorption of high energy photonsin the overlaying cover glass, AR coatings, and top surface of thesemiconductor window layer. InGaAs quantum well structures, however,provide a pathway to generate higher currents via the collection oflower energy photons. The projected 44 mA/cm² current density of theInGaAs quantum well device shown as line 720 in FIG. 7 assumes a 95%collection efficiency for the otherwise uncollected photons betweenapproximately 1.26 eV and 2.1 eV in the AM0 spectrum. Collectionefficiencies of 95% or higher are readily available in bulk III-Vsemiconductor devices, but will require increasing the optical pathlength through a 300 Å quantum well via light trapping by a factor of50-100×.

The projected open circuit voltage of the InGaAs quantum well deviceshown in FIG. 7 assumes the dark current is limited by radiativerecombination, and that the radiative recombination suppression factor(RSF) is 200. Photon recycling due to the reflection and re-absorptionof emitted photons is expected to further decrease the radiative currentdensity by over 10×, and thus should ultimately lead to RSF values wellin excess of 200 in devices with light trapping.

Accordingly, the unique material structure described herein minimizesthe dark current of InGaAs quantum wells, and when coupled with advancedlight trapping structures, provides a pathway to increase the efficiencyof single junction GaAs-based solar cells to over 30%. Record high opencircuit voltages have been demonstrated in InGaAs quantum well waveguidesolar cell structures. Higher open circuit voltages result from the useof a novel structure incorporating a wide band gap barrier layer withina heterojunction depletion region to suppress non-radiativerecombination. A dramatic reduction in the n=2 space chargerecombination is observed, allowing the n=1 saturation current densityto be extracted from a simple two-diode fit of the short circuit currentversus open circuit voltage data. Analysis suggests that thesehigh-voltage InGaAs quantum well devices are operating in a regime ofsuppressed radiative recombination. The application of advanced lighttrapping structures provides a means to both further suppress theradiative dark current and enhance the optical path length within theabsorbing layers. The resulting increases to the operating voltage andshort circuit current are projected to result in solar-electricconversion efficiencies exceeding 30%.

The illustrative embodiments of a quantum well waveguide solar celldescribed herein with reference to FIGS. 2-6 employs a single narrowenergy gap InGaAs well. However, the teachings herein are applicable tostructures employing more than one quantum well. Such multiple quantumwell structures are well-known to those ordinarily skilled in the art ofIII-V materials and devices. An extension of the structure depicted inFIG. 2 divides the single InGaAs quantum well shown into two or moreInGaAs wells, separated from each another by wider energy gap barriermaterial. The wider energy gap material can include GaAs or AlGaAs (asshown in FIG. 2), or can include wide band-gap, strain-balancingmaterial such as GaP, InGaP, or GaAsP.

Furthermore, the illustrative embodiments of a waveguide solar celldescribed herein with reference to FIGS. 2-6 employs III-V material.However, the teachings herein are applicable to similar structuresemploying other material types. For example both the narrow band gapwell and the wider band gap extended emitter, base, widow and backsurface field layers could be composed of chalcogenide materials such ascopper indium gallium (di)selenide (CIGS). According to an illustrativeembodiment, CIS or CIGS with high indium compositions is employed forthe narrow band gap well, while CGS or CIGS with high galliumcompositions are used elsewhere in the structure. CdS and other wideband gap materials can also be employed in the extended emitter and backsurface field regions. Finally, the thickness of the narrow band gapwell is not necessarily constrained in chalcogenide materials, and itdoes not need to exhibit quantum well effects. For example a well orwells of CIS or CIGS with high indium compositions can be thicker than50 nm, but are desirably still be placed within the depletion region andaway from the zone of enhanced space charge recombination.

The foregoing has been a detailed description of illustrativeembodiments of the invention. Various modifications and additions can bemade without departing from the spirit and scope of this invention. Eachof the various embodiments described above may be combined with otherdescribed embodiments in order to provide multiple features.Furthermore, while the foregoing describes a number of separateembodiments of the apparatus and method of the present invention, whathas been described herein is merely illustrative of the application ofthe principles of the present invention. For example, the illustrativeembodiments can include additional layers to perform further functionsor enhance existing, described functions. Likewise, while not shown, theelectrical connectivity of the cell structure with other cells in anarray and/or an external conduit is expressly contemplated and highlyvariable within ordinary skill. More generally, while some ranges oflayer thickness and illustrative materials are described herein. It isexpressly contemplated that additional layers, layers having differingthicknesses and/or material choices can be provided to achieve thefunctional advantages described herein. In addition, directional andlocational terms such as “top”, “bottom”, “center”, “front”, “back”,“above”, and “below” should be taken as relative conventions only, andnot as absolute. Furthermore, it is expressly contemplated that varioussemiconductor and thin films fabrication techniques can be employed toform the structures described herein. Accordingly, this description ismeant to be taken only by way of example, and not to otherwise limit thescope of this invention.

What is claimed is:
 1. A method of manufacturing a photovoltaic devicecomprising the steps of: providing a solar cell structure including asemiconductor junction depletion region and a base layer; and embeddinga single step-graded InGaAs quantum well within the base layer of thesolar cell structure, the step-graded quantum well comprising a singledownward sloping portion and a single upward sloping portion, whereineach of the upward and downward sloping portions consisting of a seriesof approximately 35 meV energy steps.
 2. The method of claim 1 whereinthe base layer comprises a wide energy-gap base layer comprising GaAs.3. The method of claim 2 further comprising the step of employing awider energy-gap material in an emitter and inserting the widerenergy-gap material into the depletion region of the solar cellstructure.
 4. The method of claim 1 wherein the single step-gradedInGaAs quantum well is synthesized by employing metal-organic chemicalvapor deposition (MOCVD).
 5. The method of claim 1 wherein the singlestep-graded InGaAs quantum well comprises a single InGaAs quantum wellhaving a thickness of approximately 33 nm.